Spinning solution



Patented Oct. 11, 1938 UNITED STATES- SPINNING SOLUTION Rudolph S. Bley, ElizabethtomTe nm, assignor to North American Rayon Corporation, New York, N. Y., a corporation of Delaware NoDrawingn Application December 2, 1937,

. Serial bio. 177,824

\ 12 Claims. (Cl. 106-40) In the manufacture of cellulosic products, such as filaments, threads, and the like, a viscose solution is continuously extruded through the minute orifices of a spinneret into a coagulating 5 or setting bath. However, since the introduction of the viscose process great troubles have been and are still experienced as far as continuous spinning is concerned due to impurities, such as, for example, precipitated cellulose particles, sullo phur and-resin particles, zinc compounds, etc., present in either the viscose solution or the spin bath. These impurities gradually contaminate the spinnerets, clog and reduce the widths of the spinneret holes with the result that filaments [5 of uneven thickness are obtained. If contamination of the spinnerets and clogging of their holes proceeds the individual filament start to tear and occasion interruption of the spinning process. By experimentation, I have found that on i0 tamination of spinnerets and clogging of spinneret holes may be overcome by spinning viscose solutions inthe presence of cation-active compounds, these compounds being produced by condensing a halogenated petroleum hydrocarbon,

25 having a chain of eight or more carbon atoms,

with a tertiary base selected from the group consisting of amines, phosphines, arsines and stibines, or with an organic sulphide selected from the group consisting of dialkyl sulphides,

I0 diaryl sulphides, and alkyl-aryl sulphides under.

substantially anhydrousconditio'ns.

Petroleum consists of complex mixtures of hydrocarbons concerning the chemical nature of which there is very little information, although 35 there are indications that all of these materials contain members of the methane series, the 'polymethylene series and the benzene series of hydrocarbons. The difierence between petroleums' of various sources resides in the proporm tions of the difiercnt types of hydrocarbons and in the chemical nature and amounts of their impurities. Pennsylvania oil, for example, contains a large proportion of methane hydrocarbons and practically no impurities of sulphur or ii nitrogen compounds. About thirty hydrocarbons have been isolated and identified with certainty.

Distillation is the principal method used in sep-' arating crude petroleum into useful components. The distilled fractions from crude petroleum so are casinghead gasoline, gasoline, kerosene, gas

oil and lighter lubricating oils (neutrals). The

residues from such distillation supply most of the lubricating oils (bright stock), petrolatum in pasty or liquid form and either paraiiin wax 5.or petroleum pitch, depending upon the nature of the crude petroleum. Kerosene is any mixture of hydrocarbons which is not volatile enough for use as gasoline in explosion motors. Cracked gasolines are rich in olefins and diolefins. Paraffin wax was originally obtained from tars from the distillation of wood, peat, and lignite, but is now obtained from petroleum, and especially from Pennsylvania paramn-base oils. Little information is available about the composition of paraflin waxes except that it consists mainly of higher 10 alkanes and only small amounts of the normal compounds; Petrolatum (Vaseline) is a pasty mixture of hydrocarbons similar to parailln while liquid petrolatum is a high boiling petroleum distillate. Ozokerite is a natural paraflin wax originating in Galicia; in bleached form it is termed ceresin.- All of these petroleum hydrocarbons may be halogenated in conventional manner in the presenceor absence of catalysts to form halogenated hydrocarbon mixtures adapted to be condensed with the tertiary bases and organic sulphides, set forth above. The hydrocarbonaceous materials i. 'e., crude petroleums, casinghead gasolines, gasolins, kerosenes, gas oil, lubricating oils, pasty and liquid petrolatums and paraflin waxes, 26 to be halogenated may first be dissolved in carbon tetrachloride, etc., and subsequently chlorine, bromine, etc., in gaseous form introduced therein until the heat of reaction abates. Halogenated compounds; containing about to 40% of 30 halogen may be obtained in this manner. However, upon prolonging the int'roduction of halogens, compounds may be obtained containing up to about 75% of a halogen, and it is to be noted that the boiling or fusing points of the raw 86 materials are either lowered .or raised by halogenation. Hydrochloric acid, hydrobromic acid, etc., formed during this reaction mustbe re-j moved, preferably byneutralization. Catalysts, such as iron, etc., may be added to the mixtures 40 to accelerate halogenation. Halogenation will also proceed more rapidly by carryin out the reaction under the influence of ultra-violet rays. The halogenation may also be performed in accordance with processes disclosed, forexamp'le, 44V

Chlorafin is a very suitable raw material for myproceu.

. rel-nary bases, capable of being condensed with the halogenated hydrocarbonaceous materials,

set, forth above, are for example: Trialkyl amines; dialkyl-aryi amines, alkyl-diaryl amines, triaryl amines, pyridine, substituted pyridines, pyridazine,' pyrimidine, pyrazine, triaaole, oxazole, tetrazole, quinoline, substituted quinolines, acridine, substituted acridines, phenanthridines,

' phenanthrolines, phenazine, picoline, substituted are obtained which are capable of preventing the incrustation of spinnerets and spinneret holes' through which viscose solutions are extruded into' picolines, trialkyljphosphines, diali'ryl-aryl phosphines, eZlkyl-diaryl phosphines, triaryl phosphines, trialkyl arsines, dialkyl-aryl arsines, aikyl-diaryl arsines, triaryl arsines, trialkyl stibiines, dialkyl-aryl stibines, triaryl stlbins, etc. Organic sulphides suitable for being condensed with these halogenated petroleum hydrocarbons are dialkyl sulphides. ,al kyl-aryl; sulphides and I diaryl sulphides. Thus, during such condensations cation-active ammonium, phosphonium,

arsonium, stibonium and sulphonium compounds ,a spin bath. Cation-active compounds are surface-active compounds which carry in the cation a hydrocarbon chain having eight or more carbon atoms. They are particularly advantageous because they may be used in neutral salt, alkaline and acidic aqueous solutions and also in hard water. In'contradistinction to cation-active compounds, anion-active compounds are surfaceactive compounds which carry in the anion a more or less extended hydrocarbon They flocculate in neutral salt, alkaline and acidic aqueous solutions, and also in 'hard water. Common soaps, sulphonated oils, etc., arean'ion-active com pounds, and thus they are unable to prevent the incrustation oi spinnerets and spinneret holes These incru'fstation inhibitors are prepared by heating a halogenated hydrocarbonaceous material oil the group, set forth above, with a tertiary amine or an organic sulphide at a moderate temperature-preferable under refluxuntil condensation is completed. Before heating the two components they may be dissolved in a suitable, inert solvent, such. as, for example, benzene, ether,v toluene, etc., i'; e., in solvents which are incapable of chemically reacting with the compounds to be} condensed. The inert solvent may subsequently be removed from the condensation products by distillation and the unreacted base or sulphide separated from the condensation products -by distillation, extraction; etc. The crude incrustation inhibitors may contain a number of diilferent condensation products which need not be separated from each other. In other words, the crude condensation productsjincrus- .tation inhibitors) containing surface-active and surface-inagetive constituents may be added for reasons of economy without further purification to viscose solutions or spin baths (setting baths). Although these cation-active halides, i. e., bromides, chlorides, fluorides and iodides, may form corresponding basesin viscose solutions and salts in spin beths,.they retainthelr surface-activity and, thusf their property of preventing incrustations. If very small amounts of these condensation'products are added to viscose solutions or spin baths the physical characteristics, such as strength pla'sticity, lustre. etc., of regeneratedf cellulose produced therefrom or therein remain unaltered. Upon increasing the amount of incrustation inhibitor in a given viscose solution or spin bath; the regenerated cellulose produced therefrom or therein, respectively, may'alter its physical characteristics, i.'e., it

may acqpire a sort-lustre, become more plastic,

lose part of its original strength, etc. Far such reasonsfthe amounts to be added to viscose solutions or spin baths must be pre-determined by experimentation. Additions of about 0.4 to 1 gram per liter-of viscose solution or spin bath are sufllcient to allow continuous spinning with? out substantially changing the inherentphysical characteristics of regenerated cellulose. 7 Although these cation-active petroleum deriva= i tives improve the spinning properties o'fany conventional viscose solution or spin bath, I have 1 found that they are especially valuable as additions to zinc-bearing spin baths, i. e., spin battn containing a zinc compound, such as, for example, zinc sulphate, these baths having 'poor spinning qualities. 1i

, Example I 7 About 10 grams of a halogenated petroleum are with about 50 grams of trietlianolamine and heated under reflux at a moderate tempera-- ture, i. e., a temperature at wlgich'the raw mate-' rials as well as condensatio' products formed therefrom remain stable, until condensation iscomplete. About 0.410 1 gram of the reddishbrown condensation product are added to one liter of a viscose solution of conventional concentfation and maturity. This solution is then extruded into an acid spin bath, such as, for example,- a glucose bath, a magnesium-zinc bath, etc. The spinnerets and'spinneret holes remain clean on prolonged spinning; Other ammonium as=well as phosphonium, arsonium, stibonium and sulphonium compounds, prepared as set forth above, may be usedWvith equal success.

Example II The cation -active compound is added to b0 the. viscose solution andthe spin bath following Examples I and H. 1

Although these examples will serve to illustrate the present invention, I do not wish to be limited to "the inhibitors and concentrations thereof recited therein, since I may make use of any cation-active ammonium, phosphonium, arsonium, stibonium or sulphonium compound prepared by condensing a halogenated material containing at least one petroleum hydrocarbon having eight or more carbon atoms in its chain se-. lected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty; and liquid petrolatums and paraffln waxes with? is tertiary amine selected from the group consist- ;ing of amines, phosphines, arsines and stibines or an organic sulphide selected from the group con', sisting of dialkyl sulphides, diaryl sulphides and alkyl-aryl sulphides under substantially. anhydrous conditions, provided. these cation-active compounds aresufliciently soluble in either viscose solutions or spin baths to furnish cations therein. 1 I Modifications. ormyinvention will readily be 7 ansaoao 1. A. spinning solution for the production artificial products comprising a viscose solution and a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of halogenated crude petroleums, halogenated gasolines. halogenated kerosenes, halogenated lubricating oils, halogen-L ated pasty petrolatums, halogenated liquid petrolatums and halogenated paraflln waxes and a tertiary base selected from the group consisting of tertiary amines, tertiary phosphines, tertiary arsines and tertiary stibines, said condensation product being s'ufllciently soluble in said viscose solution to become cation-active therein.

2. A spinning solution for the production; or artificial products comprising a viscose solution and a cation-active condensation" product of a halogenated paraiiln wax and triethanolamlne.

3. A spinning solution for the production of artificial products comprising one liter of a viscose solution and about 0.4 to 1.0 gram of 9. cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting oi halogenated crude petroleums, halogenated gasolines; kerosenes, halogenated lubricating oils, halogenated pasty petrolatums, halogenated liquid pet.- rolatums and halogenated paramn waxu and a tertiary base selected from the group consisting of tertiary amines, tertiary phosphines, tertiary arsines and tertiary stibines, said condensation product being sufliciently soluble in said viscose solution to become cation-active therein.

4.- A spinning solution for the production of artificial products comprising one liter oi a viscose solution and about 0.4 to 1.0 gramoi a ca tion-active condensation product of a halogenated paraffin wax and triethanolamine.

5. A soft-lustre regenerated cellulose containing a finely divided cation-active condensation product of a halogenated hydrocarbonaoeous ma terial selected from the group consisting of halogenated crude petroieums, halogenated gasolines,

halogenated the lustre thereof.

halogenated kerosenes, halogenated lubricating oils, halogenated pasty petrolatmns, halogenated liquid and halogenated paraiiin waxes andatertiarybaseselected iromthegroup consisting oi tertiary amines, tertiary phosphines.

tertiary arsinesandtertlarystibinesin asumcient amount to diminish the lustre thereof.

6. A soft-lustre regenerated cellulose containing-a finely divided cation-active condensation product oi. a halogenated paramn' wax and triethanolamine in a suilcient amount to diminish the lustre thereof.

7. A spinning solution for the production-of artificial products comprising a viscose solution and a cation-active condensation-product of a chlorinated paramn wax and triethanolamine.

8. A spinning solution for the production of artificial products comprising a viscose solution and a cation-active condensation product of a chicrinated paraiiin wax and .a tertiary amine, said condensation product being suiiiciently soluble in said viscose solution therein.

9. A spinning solution for the production oi. artificial products comprising one "liter of a viscose solution and about 0.4 to 1.0 gram. of a' cation-active condensation product of a. chlorin-' ated paraiiin wax and triethanolamine.

10. A spinning solution for the production of artificial products comprising one liter of a viscose solution and about 0.4 to 1.0 gram 01' .a cation-active condensation product 01' a chlorinated paraflln warand a tertiary amine, said condensation product being suiiioiently soluble in said viscose solution to become cation-active thel'eln. i

11. A soft-lustre regenerated cellulose containing a finely divided cation-active condensation product of a chlorinated paraflin wax and triethanolamine in a suillcient amount to diminish the lustre thereof. a r

12. A soft-lustre reeneratedcellulose containto become cation-active ing a-flnely divided cation-active condensation 'prodmtoiachlorlnatedparaflinwaxandatertiary mine in a to diminish RUDOLPH a. nun. 

